JP2017210550A - Water-repellent and oil-repellent resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a water-repellent and oil-repellent resin composition which can cope with a general-purpose base material, is excellent in hardness, stain resistance, appearance and solvent resistance of a coated film, and is stable by one-pack type at normal temperature.SOLUTION: A water-repellent and oil-repellent resin composition used in one-pack type contains a polyol resin (A) having a fluorine atom and a graft chain containing a dimethylsiloxane skeleton, at least one combination selected from a combination of a melamine resin (B-1) and a sulfonic acid catalyst (C-1) and a combination of a block isocyanate resin (B-2) and a metal catalyst (C-2), and a water-repellent silica filler (D).SELECTED DRAWING: None

Description

  The present invention relates to a water / oil repellent resin composition.

  Conventionally, a resin composition intended to reduce the burden of cleaning by providing a water / oil repellent functional layer on the outermost surface of interior furniture, water-related kitchen-related products, bath-related products, etc. Has been proposed.

  For example, Patent Document 1 discloses that the surface is uneven by a chemical vapor deposition method using a fluorine compound having 10 to 6 carbon atoms and a perfluoroalkyl group having 1 to 6 carbon atoms at the end and no oxygen atom as a deposition source. A method for forming a water / oil repellent layer having a surface has been proposed.

  Further, Patent Document 2 discloses an acrylic resin having a functional group containing a dimethylsiloxane skeleton, an alkoxysilyl group, and a hydroxyl group, and at least one selected from an amino resin and an isocyanate resin as a crosslinking agent and a silicate hydrolyzate. A water / oil repellent resin composition to be contained has been proposed.

Japanese Patent Laying-Open No. 2015-44181 JP 2007-314607 A

  However, in Patent Document 1, advanced processing such as etching and vapor deposition of a fluorine compound is required on the surface of the member in order to achieve water and oil repellency. Therefore, there is room for improvement in the hardness (abrasion resistance) of the outermost layer. In addition, since the base material is limited and the cost is high, there is a problem that it lacks versatility.

  In Patent Document 2, since a silicate hydrolyzate is contained, a coating film having high hardness is formed. However, since the silicate hydrolyzate is moisture-cured at room temperature, it is stable when the paint is made into one liquid. It is very difficult to secure sex.

  In addition, in the water / oil repellent resin composition, in addition to the hardness of the coating film and the stability when the coating is made into one liquid, it is also desired that the coating film has good stain resistance, appearance, and solvent resistance. .

  The present invention has been made in view of the circumstances as described above, and can be used for general-purpose substrates, and has excellent hardness, stain resistance, appearance, and solvent resistance of a coating film, and is stable at one liquid at room temperature. An object of the present invention is to provide a water / oil repellent resin composition.

  In order to solve the above-mentioned problems, the water / oil repellent resin composition of the present invention is a water / oil repellent resin composition used in a single solution, has a fluorine atom, and contains a dimethylsiloxane skeleton. From a combination of a polyol resin (A) having a graft chain and a melamine resin (B-1) and a sulfonic acid catalyst (C-1), or a combination of a blocked isocyanate resin (B-2) and a metal catalyst (C-2) It contains at least one selected combination and a water-repellent silica filler (D).

  According to this invention, it can respond to a general purpose base material, is excellent in the hardness of a coating film, stain resistance, an external appearance, and solvent resistance, and is stable at one liquid at normal temperature.

  Hereinafter, embodiments of the present invention will be described.

  The polyol resin (A) used in the water / oil repellent resin composition of the present embodiment is a main agent for realizing water / oil repellency.

  The polyol resin (A) has a fluorine chain and a graft chain containing a dimethylsiloxane skeleton. The polyol resin (A) is, for example, a copolymer containing a monomer having a fluorine atom, a monomer having a hydroxyl group, and a reactive silicone as copolymerized units.

  As the monomer having a fluorine atom, a fluorine-containing monomer usually used as a fluororesin raw material can be used. Specifically, for example, tetrafluoroethylene (TFE), vinylidene fluoride (VdF), hexafluoropropylene (HFP), chlorotrifluoroethylene (CTFE), vinyl fluoride (VF), perfluoro (alkyl vinyl ether) ( PAVE), a monomer in which a fluoroalkyl group and a polymerizable unsaturated group are linked by an ether bond or an ester bond. These may be used alone or in combination of two or more.

  Examples of the monomer having a hydroxyl group include 2-hydroxyethyl vinyl ether, 3-hydroxypropyl vinyl ether, 2-hydroxypropyl vinyl ether, 2-hydroxy-2-methylpropyl vinyl ether, 4-hydroxybutyl vinyl ether, 4-hydroxy-2. Hydroxyl group-containing vinyl ethers such as methylbutyl vinyl ether, 5-hydroxypentyl vinyl ether, 6-hydroxyhexyl vinyl ether; hydroxyl group-containing allyl ethers such as 2-hydroxyethyl allyl ether, 4-hydroxybutyl allyl ether, glycerol monoallyl ether; 2 -Hydroxyacrylates such as hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate Kill (meth) acrylates. These may be used alone or in combination of two or more.

Examples of the reactive silicone include those represented by the following formula (1) or formula (2).
_{^{R 1 - [Si (CH 3}} ) 2 -O] n -Si (CH 3) 2 -R 2 ··· (1)
(In Formula (1), R ¹ is an alkyl group having 1 to 6 carbon atoms, — (CH ₂ ) _r —OOC (CH ₃ ) C═CH ₂ or —CH═CH ₂ , and R ² is — (CH _{2) r} -OOC (CH ₃₎ a C = CH ₂ or -CH = CH ₂ .n is 1 to 420, r is 1-6.)
R ² —Si [OSi (CH ₃ ) ₃ ] ₃ (2)
(R ² in formula (2) is as defined above.)
As the reactive silicone represented by the above formula (1) or (2), for example, polydimethylsiloxane having methacrylic modification at one end, polydimethylsiloxane having acrylic modification at one end, and dimethylmodified polydimethylsiloxane at both ends Siloxane or the like can be used. These reactive silicones may be used alone or in combination of two or more.

Further, the reactive silicone may be represented by the following formulas (3), (4), (5), (6).
_{CH 2 = C (CH 3)} -COO-C 3 H 6 - [Si (CH 3) 2 -O] m -Si (CH 3) 2 -R 3 ··· (3)
(Here, R ³ represents an alkyl group having 1 to 6 carbon atoms. M represents an integer of 1 to 250.)
_{CH 2 = CH-COO-C} 3 H 6 - [Si (CH 3) 2 -O] p -Si (CH 3) 2 -R 4 ··· (4)
(Here, R ⁴ represents an alkyl group having 1 to 6 carbon atoms. P represents an integer of 1 to 250.)
^{_{R 5 -C 3 H 6 - [}} Si (CH 3) 2-O] q -C 3 H 6 -R 5 ··· (5)
(Here, R ⁵ represents —OCOC (CH ₃ ) ═CH _2. Q represents an integer of 1 to 250.)
_{CH 2 = C (CH 3)} COO-C 3 H 6 Si [OSi (CH 3) 3] 3 ··· (6)
A polyol resin (A) is good also as a copolymer in combination with another monomer as needed with the monomer which has said fluorine atom, the monomer which has a hydroxyl group, and reactive silicone. Examples of other monomers include alkyl vinyl ethers, alkyl allyl ethers, methacrylic acid esters and acrylic acid esters, carboxylic acid vinyl esters, and olefins. These may be used alone or in combination of two or more.

  The polyol resin (A) contains a fluorine atom-containing monomer-derived structure in the range of 1 to 70% by mass, for example.

  The polyol resin (A) contains a reactive silicone-derived structure in the range of, for example, 10 to 90% by mass.

  The polyol resin (A) has a hydroxyl value in the range of, for example, 5 to 200 mgKOH / g.

  Specific examples of the polyol resin (A) include ZX series (ZX-001, ZX-007-C, ZX-017, ZX-022, ZX-022-H, etc., manufactured by T & KTOKA Corporation), F-clear series ( KD-270F1, KD-270, KD-200, KD3000, etc. manufactured by Kanto Denka Co., Ltd.). These may be used alone or in combination of two or more.

  The polyol resin (A) is preferably 10 to 70% by mass, more preferably 25 to 65%, based on the coating film, as the resin content in the coating film after curing of the water / oil repellent resin composition of the present embodiment. It is contained in the range of mass%. When the content is 10% by mass or more, the water / oil repellency of the coating film is good, and when the content is 70% by mass or less, a decrease in compatibility with solvents and other resins is suppressed. The film forming property is improved, and the hardness and water / oil repellency are improved.

  The melamine resin (B-1) used in the water / oil repellent resin composition of the present embodiment undergoes a condensation reaction with the main component polyol resin (A) to cure the coating film.

  Examples of the melamine resin (B-1) include partially etherified or fully etherified melamine resins obtained by etherifying part or all of methylol groups of methylolated melamine with monohydric alcohol having 1 to 8 carbon atoms. It is done. These may be used alone or in combination of two or more. Examples of the monohydric alcohol having 1 to 8 carbon atoms include methyl alcohol, ethyl alcohol, n-propyl alcohol, i-propyl alcohol, n-butyl alcohol, i-butyl alcohol, 2-ethylbutanol, and 2-ethyl. Examples include hexanol.

  Specific examples of the melamine resin (B-1) include, for example, methylated melamine resin: Super Becamine L-105-60, butylated melamine resin: Super Becamine J-820-60, L-109-65, L -117-60, L-127-60, 13-548, G-821-60, L-110-60, L-125-60, L-166-60B (manufactured by DIC Corporation), Cymel 202, Cymel 232, Cymel 235, Cymel 238, Cymel 254, Cymel 266, Cymel 267, Cymel 272, Cymel 285, Cymel 301, Cymel 303, Cymel 325, Cymel 327, Cymel 350, Cymel 370, Cymel 701, Cymel 703, Cymel 1141 (Nippon Cytec) Made by Industries , Uban 20SE60, Uban 21R, Uban 22R, Uban 122, Uban 125, Uban 128, Uban 220, Uban 225, Uban 228, Uban 28-60, Uban 2020, Uban 60R, Uban 62E, Uban 62E, Uban 360, Uban 165 Uban 166-60, Uban 169, Uban 2061 (manufactured by Mitsui Chemicals, Inc.) and the like.

  The melamine resin (B-1) is preferably 3 to 40% by mass, more preferably 5%, based on the coating film, as the resin content in the coating film after curing of the water / oil repellent resin composition of the present embodiment. It is contained in a range of ˜30% by mass, more preferably 10% to 25% by mass. When the content is 3% by mass or more, the hardness of the coating film is good, and when the content is 40% by mass or less, unreacted melamine resin remains in the coating film and the film formability is lowered. This can be suppressed and the hardness and water / oil repellency are improved.

  In the water / oil repellent resin composition of the present embodiment, the sulfonic acid catalyst (C-1) is used as a curing accelerator for the melamine resin (B-1).

  Examples of the sulfonic acid catalyst (C-1) include sulfonic acid compounds such as p-toluenesulfonic acid, dodecylbenzenesulfonic acid, dinonylnaphthalenesulfonic acid, dinonylnaphthalenedisulfonic acid, and neutralized amines thereof. . The amine in the amine neutralized product of the sulfonic acid compound may be any of primary amine, secondary amine, and tertiary amine. These may be used alone or in combination of two or more. Among these, in view of coating stability, reaction promoting effect, obtained coating film properties, and the like, an amine neutralized product of p-toluenesulfonic acid and an amine neutralized product of dodecylbenzenesulfonic acid are preferable.

  Specific examples of the sulfonic acid compound in the sulfonic acid catalyst (C-1) include dinonylnaphthalene disulfonic acid: Nacure 155, Nacure 3525, Nacure X49-110, Nacure 1051, dodecylbenzene sulfonic acid: Nacure 5076, Nacure 5225, Nacure 5528, Nacure 5925, p. -Toluenesulfonic acid: Nacure 2017, Nacure 2500 (manufactured by Enomoto Kasei Co., Ltd.) and the like.

  The content of the sulfonic acid catalyst (C-1) in the water / oil repellent resin composition of the present embodiment is preferably 0.1 to 5.0% by mass, more preferably 0, based on the polyol resin (A). 0.5 to 4.5% by mass, more preferably 1.0 to 3.5% by mass. When the content is 0.1% by mass or more, the hardness of the coating film is good, and when the content is 5.0% by mass or less, the reaction rate is too high and cracks are generated in the coating film. Is suppressed, film formability is improved, and hardness and water / oil repellency are improved.

  The blocked isocyanate resin (B-2) used in the water / oil repellent resin composition of the present embodiment undergoes a condensation reaction with the main polyol resin (A) to cure the coating film.

  Examples of the isocyanate part of the blocked isocyanate resin (B-2) include TDI, HDI, XDI, hydrogenated XDI, and IPDI, and modified TMP adducts, isocyanurates, biurets, and allophanates. Is mentioned. These may be used alone or in combination of two or more.

  Examples of the blocking agent for the blocked isocyanate resin (B-2) include lactams such as ε-caprolactam, δ-valerolactam, γ-butyrolactam, β-propiolactam; methanol, ethanol, propanol, butanol, ethylene glycol, Alcohols such as methyl cellosolve, butyl cellosolve, methyl carbitol, benzyl alcohol, phenyl cellosolve, furfuryl alcohol, cyclohexanol; butylphenols such as phenol, cresol, xylenol, ethylphenol, o-isopropylphenol, p-tert-butylphenol, p -Tert-octylphenol, nonylphenol, dinonylphenol, styrenated phenol, oxybenzoate, thymol, p-naphthol, p Phenols such as nitrophenol and p-chlorophenol; active methylenes such as dimethyl malonate, diethyl malonate, methyl acetoacetate, ethyl acetoacetate and acetylacetone; mercaptans such as butyl mercaptan, thiophenol and tert-dodecyl mercaptan; Amines such as diphenylamine, phenylnaphthylamine, aniline, carbazole; acid amides such as acetanilide, acetanisidide, acetic acid amide, benzamide; acid imides such as succinimide, maleic imide; imidazole, 2-methylimidazole, 2-ethyl Imidazoles such as imidazole; Ureas such as urea, thiourea and ethyleneurea; Carbamates such as phenyl N-phenylcarbamate and 2-oxazolidone: Ethyleneimine, polyester Examples thereof include imine compounds such as tylene imine; oxime compounds such as formaldoxime, acetaldoxime, acetooxime, methylethylketoxime, methylisobutylketoxime, cyclohexanone oxime; and bisulfites such as sodium bisulfite and potassium bisulfite. These may be used alone or in combination of two or more.

  Specifically as block isocyanate resin (B-2), for example, Sumidur BL3175, Sumidur BL3575 (manufactured by Sumika Bayer Urethane Co., Ltd.), Barnock D-500, Barnock D-550, Barnock DB-980K (manufactured by DIC Corporation) ), Takenate B-830, Takenate B-815N, Takenate B-842N, Takenate B-870N, Takenate B-882N, Takenate B-890, Takenate B-7005, Takenate B-7030, Takenate B-7005, B-5010 , PW-2400 (Mitsui Chemicals), Duranate MF-K60B, Duranate SBN-70D, Duranate MF-B60B, Duranate 17B-60P, Duranate TPA-B80E, Duranate 402-B80B (manufactured by Asahi Kasei Co., Ltd.), and the like.

  The blocked isocyanate resin (B-2) is preferably 5 to 50% by mass, more preferably, based on the coating film, as the resin content in the coating film after curing of the water / oil repellent resin composition of the present embodiment. It is contained in the range of 8 to 45% by mass, more preferably 10 to 40% by mass. When this content is 5% by mass or more, the hardness of the coating film is good, and when this content is 50% by mass or less, excess isocyanate reacts with moisture in the air to cause hardness and water repellency. It can suppress that oil-repellent performance falls.

  In the water / oil repellent resin composition of the present embodiment, the metal catalyst (C-2) is used as a curing accelerator for the blocked isocyanate reaction. Specifically, the metal catalyst (C-2) is a metal chelate compound.

  Examples of the metal of the metal chelate compound include aluminum, zinc, cobalt, nickel, manganese, copper, titanium, and bismuth. These may be used alone or in combination of two or more.

  Examples of the chelate ligand of the metal chelate compound include acetylacetone, 3,5-heptanedione, 1,1,1-trifluoro-2,4-pentanedione, 1,1,1,5,5,5- Β-diketones such as hexafluoro-2,4-pentanedione; β-ketoesters such as methyl acetoacetate, ethyl acetoacetate, n-propyl acetoacetate, isopropyl acetoacetate; malons such as dimethyl malonate and diethyl malonate Acid diesters; β-ketoamides such as acetoacetanilide; and carboxylic acids such as acetic acid, propionic acid, butanoic acid, pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, and 2-ethylhexanoic acid. These may be used alone or in combination of two or more.

  When the metal of the metal chelate compound is zinc, examples of the metal chelate compound include zinc bisacetylacetonate, zinc bis3,5-heptanedionate, zinc bis1,1,1-trifluoro-2,4- Pentandionate, zinc bis-1,1,1,5,5,5-hexafluoro-2,4-pentanedionate, methyl zinc bisacetoacetate, ethyl zinc bisacetoacetate, zinc bisacetoacetate, isopropyl zinc bisacetoacetate , Zinc bismalonate dimethyl, zinc bismalonate diethyl, zinc bisacetoacetanilide, zinc bisacetic acid, zinc bispropionic acid, zinc bisbutanoic acid, zinc bispentanoic acid, zinc bishexanoic acid, zinc bisheptanoic acid, zinc bisoctanoic acid, zinc bis-2-ethyl And hexanoic acid.

  The content of the metal catalyst (C-2) in the water / oil repellent resin composition of the present embodiment is preferably 0.1 to 5.0% by mass, more preferably 0.00%, based on the polyol resin (A). It is 5-4.5 mass%, More preferably, it is the range of 1.0-3.5 mass%. When the content is 0.1% by mass or more, the hardness of the coating film is good, and when the content is 5.0% by mass or less, the reaction rate is too high and cracks are generated in the coating film. Is suppressed, film formability is improved, and hardness and water / oil repellency are improved.

  In the water / oil repellent resin composition of the present embodiment, a combination of the melamine resin (B-1) and the sulfonic acid catalyst (C-1), or the block isocyanate resin (B-2) and the metal catalyst (C-2). A combination may be used individually by 1 type and may be used in combination of 2 or more type.

  The water-repellent silica filler (D) used in the water- and oil-repellent resin composition of the present embodiment can improve the hardness of the coating film by containing this.

  Here, the water repellency of the water-repellent silica filler (D) means that the silica filler is made water-repellent by, for example, polymerizing using a material having a water-repellent functional group or applying a water-repellent treatment to the surface. It means to do. Thus, since the surface has water repellency, water and oil repellency can be maintained. The average particle diameter of the silica filler (D) is preferably 0.01 to 20 μm. When the average particle size is 20 μm or less, a decrease in gloss of the coating film can be suppressed. Here, the average particle diameter of the silica filler (D) is determined by, for example, using a commercially available laser diffraction / scattering type particle size distribution measuring device and measuring the particle size distribution by the laser diffraction / scattering method to determine the median diameter (d50 , Volume basis).

  Specific examples of the water-repellent silica filler (D) include Tospearl 120, Tospearl 130, Tospearl 145, Tospearl 2000B, Tospearl 1110, Tospearl 240 (manufactured by Momentave Performance Materials Co., Ltd.), Organosilica Sol IPA-ST IPA-ST-L, IPA-ST-ZL, IPA-ST-UP, EG-ST, EG-ST-ZL, DMAC-ST, DMAC-ST-ZL, PGM-ST, MEK-ST, MEK-ST -L, MEK-ST-ZL, MIBK-ST, EAC-ST, NBAC-ST (manufactured by Nissan Chemical Industries, Ltd.) and the like.

  The water-repellent silica filler (D) is preferably 1 to 20% by mass, more preferably 2 to 15% with respect to the coating film in the coating film after curing of the water / oil repellent resin composition of the present embodiment. It is contained in the range of 3% by mass, more preferably 3-10% by mass. When this content is 1% by mass or more, the hardness of the coating film is good, and when this content is 20% by mass or less, it is possible to suppress a decrease in film formability due to a decrease in resin content, Hardness and water / oil repellency are improved.

  The water / oil repellent resin composition of the present embodiment can be diluted by blending various organic solvents for ease of handling. Examples of such an organic solvent include lower aliphatic alcohols such as methanol, ethanol, isopropanol, n-butanol and isobutanol; ethylene glycol derivatives such as ethylene glycol, ethylene glycol monobutyl ether and ethylene glycol monoethyl ether acetate; Examples include diethylene glycol derivatives such as diethylene glycol and diethylene glycol monobutyl ether; and hydrophilic organic solvents such as diacetone alcohol. These may be used alone or in combination of two or more. Along with these hydrophilic organic solvents, toluene, xylene, ethyl acetate, butyl acetate, methyl ethyl ketone, methyl isobutyl ketone, methyl ethyl ketoxime and the like may be used in combination.

  In the water / oil repellent resin composition of the present embodiment, other components than the above-described components are blended in order to improve physical properties, paintability, etc. within a range not impairing the effect. be able to. Examples of such other components include antibacterial agents, antifungal agents, matting agents, antifoaming agents, antisettling agents, leveling agents, dispersants, heat stabilizers, ultraviolet absorbers, wax components, and the like. .

  The water / oil repellent resin composition of the present embodiment can be prepared, for example, as a one-component composition by mixing each compounding component by a conventional method. The water / oil repellent resin composition of the present embodiment is stable in a single solution at room temperature.

  The water / oil repellent resin composition of the present embodiment can form a water / oil repellent cured coating film on the surface of the substrate by applying and curing on the surface of the substrate. The cured coating film using the water / oil repellent resin composition of the present embodiment is excellent in the hardness, stain resistance, appearance, and solvent resistance of the coating film. The conditions for curing after applying the water / oil repellent resin composition of the present embodiment to the substrate surface are not particularly limited, but heating is preferable. The heating temperature is preferably 80 to 200 ° C.

  The water / oil repellent resin composition of the present embodiment can correspond to a general-purpose substrate, and is not particularly limited as a substrate to which the water / oil repellent resin composition of the present embodiment is applied. , Metal, plastic or glass members, wood, cloth and the like. Although the shape of the said member is not specifically limited, For example, a plate-shaped member etc. are mentioned.

  The thickness of the coating film on the substrate surface by the water / oil repellent resin composition of the present embodiment is preferably 1 to 50 μm, more preferably 3 to 30 μm in terms of the thickness after curing.

  When forming the coating film with the water / oil repellent resin composition of the present embodiment, the number of times of applying the water / oil repellent resin composition of the present embodiment to the substrate surface is not particularly limited. May be twice or more.

  The apparatus and method for applying the water- and oil-repellent resin composition of the present embodiment to the substrate surface are not particularly limited. For example, conventionally known flow coater, roll coater, spraying method, airless spray method , Air spray method, brush coating, trowel coating, dipping method, pulling method, nozzle method, winding method, sink method, piling, patching method and the like. These apparatuses and methods may be automated, or the water / oil repellent resin composition of the present embodiment may be manually applied.

  EXAMPLES Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to these examples. In the following description, “part” means “part by mass” and “%” means “% by mass” unless otherwise specified.

The following components were used in the examples and comparative examples.
Polyol resin (A)
F Clear KD3000 (NV = 29-31%) manufactured by Kanto Denka Kogyo Co., Ltd.
Melamine resin (B-1)
L-125-60 made by DIC Corporation
Block isocyanate resin (B-2)
Asahi Kasei Corporation Duranate TPA-B80E
Sulfonic acid catalyst (C-1)
Nacure 2107 manufactured by Enomoto Kasei Co., Ltd.
Metal catalyst (C-2)
Bismuth carboxylate XK628 manufactured by Enomoto Kasei Co., Ltd.
Water repellent silica filler (D)
Tospearl 120 manufactured by Momentave Performance Materials
Thinner Liquid fluorine coating agent 1 in which ethyl acetate and butyl acetate are mixed at a volume ratio of 1: 1
Unidyne TG6071 made by Daikin Industries, Ltd.
Fluorine coating agent 2
S Coat S-680 manufactured by AGC Semi Chemical Co., Ltd.
Fluorine coating agent 3
Novec2702 from 3M
Fluorine coating agent 4
KY-164 manufactured by Shin-Etsu Chemical Co., Ltd.
An alumite plate 15 cm × 7 cm × 1.5 cm (manufactured by Nippon Test Panel Co., Ltd.) was used as the substrate.
Example 1
While stirring 60 parts of polyol resin (A) and 23 parts of thinner with a disper, 10 parts of melamine resin (B-1) was added. To this mixed solution, 2 parts of a sulfonic acid catalyst (C-1) and 5 parts of a water-repellent silica filler (D) were added and dispersed with a disper for 15 minutes to obtain a paint. This paint was applied to an alumite substrate using air spray so that the film thickness became 10 μm, and then cured at 150 ° C. for 30 minutes with a dryer to obtain a coating sample.
(Example 2)
While stirring 60 parts of the polyol resin (A) and 18 parts of thinner with a disper, 15 parts of the blocked isocyanate resin (B-2) was added. To this mixed solution, 2 parts of a metal catalyst (C-2) and 5 parts of a water-repellent silica filler (D) were added, and dispersed for 15 minutes with a disper to obtain a paint. This paint was applied to an alumite substrate using air spray so that the film thickness became 10 μm, and then cured at 150 ° C. for 30 minutes with a dryer to obtain a coating sample.
(Example 3)
While stirring 60 parts of polyol resin (A) and 22 parts of thinner with a disper, 5 parts of melamine resin (B-1) and 6 parts of blocked isocyanate resin (B-2) were added. To this mixed solution, 1 part of a sulfonic acid catalyst (C-1), 1 part of a metal catalyst (C-2) and 5 parts of a water-repellent silica filler (D) were added and dispersed with a disper for 15 minutes to obtain a paint. . This paint was applied to an alumite substrate using air spray so that the film thickness became 10 μm, and then cured at 150 ° C. for 30 minutes with a dryer to obtain a coating sample.
Example 4
8 parts of melamine resin (B-1) was added while stirring 50 parts of polyol resin (A) and 35.5 parts of thinner with a disper. To this mixed solution, 1.5 parts of a sulfonic acid catalyst (C-1) and 5 parts of a water-repellent silica filler (D) were added and dispersed with a disper for 15 minutes to obtain a paint. This paint was applied to an alumite substrate using air spray so that the film thickness became 10 μm, and then cured at 150 ° C. for 30 minutes with a dryer to obtain a coating sample.
(Example 5)
13 parts of melamine resin (B-1) was added while stirring 65 parts of polyol resin (A) and 14.5 parts of thinner with a disper. To this mixed solution, 2.5 parts of a sulfonic acid catalyst (C-1) and 5 parts of a water-repellent silica filler (D) were added and dispersed with a disper for 15 minutes to obtain a paint. This paint was applied to an alumite substrate using air spray so that the film thickness became 10 μm, and then cured at 150 ° C. for 30 minutes with a dryer to obtain a coating sample.
(Example 6)
While stirring 50 parts of polyol resin (A) and 30.5 parts of thinner with a disper, 13 parts of blocked isocyanate resin (B-2) was added. To this mixed solution, 1.5 parts of a metal catalyst (C-2) and 5 parts of a water-repellent silica filler (D) were added and dispersed with a disper for 15 minutes to obtain a paint. This paint was applied to an alumite substrate using air spray so that the film thickness became 10 μm, and then cured at 150 ° C. for 30 minutes with a dryer to obtain a coating sample.
(Example 7)
While stirring 65 parts of polyol resin (A) and 9.5 parts of thinner with a disper, 18 parts of blocked isocyanate resin (B-2) was added. To this mixed solution, 2.5 parts of a metal catalyst (C-2) and 5 parts of a water-repellent silica filler (D) were added and dispersed with a disper for 15 minutes to obtain a paint. This paint was applied to an alumite substrate using air spray so that the film thickness became 10 μm, and then cured at 150 ° C. for 30 minutes with a dryer to obtain a coating sample.
(Example 8)
While stirring 60 parts of polyol resin (A) and 17.5 parts of thinner with a disper, 15 parts of melamine resin (B-1) was added. To this mixed solution, 2.5 parts of a sulfonic acid catalyst (C-1) and 5 parts of a water-repellent silica filler (D) were added and dispersed with a disper for 15 minutes to obtain a paint. This paint was applied to an alumite substrate using air spray so that the film thickness became 10 μm, and then cured at 150 ° C. for 30 minutes with a dryer to obtain a coating sample.
Example 9
While stirring 60 parts of polyol resin (A) and 20 parts of thinner with a disper, 10 parts of melamine resin (B-1) was added. To this mixed solution, 2 parts of a sulfonic acid catalyst (C-1) and 8 parts of a water-repellent silica filler (D) were added and dispersed with a disper for 15 minutes to obtain a paint. This paint was applied to an alumite substrate using air spray so that the film thickness became 10 μm, and then cured at 150 ° C. for 30 minutes with a dryer to obtain a coating sample.
(Comparative Example 1)
While stirring 60 parts of polyol resin (A) and 25 parts of thinner with a disper, 10 parts of melamine resin (B-1) was added. To this mixed solution, 5 parts of a water-repellent silica filler (D) was added and dispersed with a disper for 15 minutes to obtain a paint. This paint was applied to an alumite substrate using air spray so that the film thickness became 10 μm, and then cured at 150 ° C. for 30 minutes with a dryer to obtain a coating sample.
(Comparative Example 2)
While stirring 60 parts of the polyol resin (A) and 20 parts of thinner with a disper, 15 parts of the blocked isocyanate resin (B-2) was added. To this mixed solution, 5 parts of a water-repellent silica filler (D) was added and dispersed with a disper for 15 minutes to obtain a paint. This paint was applied to an alumite substrate using air spray so that the film thickness became 10 μm, and then cured at 150 ° C. for 30 minutes with a dryer to obtain a coating sample.
(Comparative Example 3)
While stirring 60 parts of the polyol resin (A) and 23 parts of thinner with a disper, 15 parts of the blocked isocyanate resin (B-2) was added. 2 parts of a metal catalyst (C-2) was added to this mixed solution and dispersed with a disper for 15 minutes to obtain a paint. This paint was applied to an alumite substrate using air spray so that the film thickness became 10 μm, and then cured at 150 ° C. for 30 minutes with a dryer to obtain a coating sample.
(Comparative Example 4)
A paint was obtained by adjusting Unidyne TG6071 made by Daikin Industries, Ltd., which is a fluorine-based coating agent 1, with a thinner (mixed solution of ethyl acetate and butyl acetate in a volume ratio of 1: 1) so that NV = 15%. This paint was applied to an alumite substrate with an air spray with a film thickness of 10 μm, and then cured with a dryer at 150 ° C. for 30 minutes to obtain a coating sample.
(Comparative Example 5)
A coating material prepared by adjusting SFCcoat S-680 manufactured by AGC Semi-Chemical Co., Ltd., which is a fluorine coating agent 2, with a thinner (mixed solution of ethyl acetate and butyl acetate in a volume ratio of 1: 1) so that NV = 15%. Got. This paint was applied to an alumite substrate with an air spray with a film thickness of 10 μm, and then cured with a dryer at 150 ° C. for 30 minutes to obtain a coating sample.
(Comparative Example 6)
A coating material was obtained by adjusting 3M Novec 2702, which is fluorine-based coating agent 3, with a thinner (mixed solution of ethyl acetate and butyl acetate in a volume ratio of 1: 1) so that NV = 15%. This paint was applied to an alumite substrate with an air spray with a film thickness of 10 μm, and then cured with a dryer at 150 ° C. for 30 minutes to obtain a coating sample.
(Comparative Example 7)
The coating material was obtained by adjusting Shin-Etsu Chemical Co., Ltd. KY-164, which is a fluorine-based coating agent 4, with a thinner (mixed solution of ethyl acetate and butyl acetate in a volume ratio of 1: 1) so that NV = 15%. . This paint was applied to an alumite substrate with an air spray with a film thickness of 10 μm, and then cured with a dryer at 150 ° C. for 30 minutes to obtain a coating sample.
(Comparative Example 8)
An uncoated alumite substrate was used.
<Evaluation>
[Paint stability]
The coating materials of Examples and Comparative Examples were stored in a dryer at 50 ° C. for 30 days, and the fluidity of the coating materials was visually confirmed and judged according to the following criteria.
○: Fluidity ×: Gelation [pencil hardness]
Pencil scratch value was taken by hand scribing method, and H or higher was regarded as an acceptable line.
[Contamination resistance]
Using oil-based magic ink manufactured by Teranishi Chemical Industry Co., Ltd., a 5 cm straight line was drawn on the surface of the coated sample. After that, the felt was wiped off by using felt. Judgment was made according to the following criteria due to the difference in antifouling performance.
A: The repelling property of the magic is good visually, and the magic mark can be removed with a light force.
○: The repelling property of the magic was good visually, and the magic marks were also clean.
(Triangle | delta): There was magic repellency visually and the magic trace was also taken.
X: There is no magic repellency visually, and a magic mark cannot be taken.
[appearance]
The surface smoothness was visually confirmed while illuminating the painted sample obliquely, and judged according to the following criteria.
○: Smoothness of the coating film surface.
Δ: The coating film surface is slightly wavy.
X: The coating film surface is wavy.
[Solvent resistance]
A cotton swab containing a methanol solvent was used to perform 100 reciprocating rubbing tests on the coating film of the paint sample, visually observing the film appearance of the test site while exposing the test surface to light, and judging according to the following criteria: .
A: The film appearance is not visually changed.
○: The film appearance was slightly changed by gloss.
Δ: The film appearance was visually changed.
X: It was confirmed visually that the film was dissolved.

  The evaluation results are shown in Tables 1 and 2.

  As shown in Table 1, Examples 1 to 9 were excellent in paint stability, pencil hardness, stain resistance, appearance, and solvent resistance of the cured coating film formed on the alumite substrate. In particular, the blends of Examples 1, 3, and 7 were very excellent in pencil hardness and stain resistance. In Example 8 in which the amount of the melamine resin (B-1) and the sulfonic acid catalyst (C-1) was increased, the pencil hardness was even higher.

  On the other hand, as shown in Table 2, in Comparative Examples 1 and 2 in which neither the sulfonic acid catalyst (C-1) nor the metal catalyst (C-2) was blended, the coating film was not solidified, Contamination resistance and solvent resistance decreased. Comparative Example 3 in which the water-repellent silica filler (D) was not blended was inferior in pencil hardness and stain resistance. Moreover, the comparative examples 4-7 which are the conventional antifouling paints were inferior in the external appearance of the coated product on an alumite base material, and the pencil hardness was also low.

As described above, a combination of a polyol resin (A) having a fluorine atom and a graft chain containing a dimethylsiloxane skeleton, a melamine resin (B-1) and a sulfonic acid catalyst (C-1), or a blocked isocyanate The composition containing at least one combination selected from the combination of the resin (B-2) and the metal catalyst (C-2) and the water-repellent silica filler (D) has a pencil hardness and stain resistance of the coating film. Excellent in properties, appearance, and solvent resistance, and stable in a single solution at room temperature.

Claims (3)

A water / oil repellent resin composition used in a single solution,
A polyol resin (A) having a fluorine atom and having a graft chain containing a dimethylsiloxane skeleton;
At least any combination selected from a combination of a melamine resin (B-1) and a sulfonic acid catalyst (C-1), or a combination of a blocked isocyanate resin (B-2) and a metal catalyst (C-2);
A water / oil repellent resin composition comprising a water repellent silica filler (D).   The water / oil repellent resin composition according to claim 1, comprising a combination of the melamine resin (B-1) and the sulfonic acid catalyst (C-1). The water / oil repellent resin composition according to claim 1, comprising a combination of the blocked isocyanate resin (B-2) and the metal catalyst (C-2).